Effect of Molecular Organization on the Properties of Fractionated Lignin-Based Thiol–Ene Thermoset Materials

In this study, the combination of sequential solvent fractionation of technical Kraft lignin was followed by allylation of most OH functionalities to give highly functional thermoset resins. All lignin fractions were highly functionalized on the phenolic (≥95%) and carboxylic acid OH (≥85%) and to a significant extent on the aliphatic OH moieties (between 43 and 75%). The resins were subsequently cross-linked using thiol–ene chemistry. The high amount of allyl functionalities resulted in a high cross-link density. Dynamic mechanical analysis measurements showed that the thioether content, directly related to the allyl content, strongly affects the performance of these thermosets with a glass transition temperature ($T_g$) between 81 and 95 °C and with a storage modulus between 1.9 and 3.8 GPa for all thermosets. The lignin fractions and lignin-based thermosets’ morphology, at the nanoscale, was studied by wide-angle X-ray scattering measurements. Two π–π stacking interactions were observed: sandwich (≈4.1–4.7 Å) and T-shaped (≈5.5–7.2 Å). The introduction of allyl functionalities weakens the T-shaped π–π stacking interactions. A new signal corresponding to a distance of ≈3.5 Å was observed in lignin-based thermosets, which was attributed to a thioether organized structure. At the same time, a lignin superstructure was observed with a distance/size corresponding to 7.9–17.5 Å in all samples

Impact of lignin source on the performance of thermoset resins

A series of different technical hardwood lignin-based resins have been successfully synthesized, characterized, and utilised to produce thiol-ene thermoset polymers. Firstly, technical lignin was fractionated and allylated, whereafter it was crosslinked with a trifunctional thiol. Structural and morphological characteristics of the lignin fractions were studied by $^{1}$H NMR, $^{31}$P NMR, SEC, FTIR, DSC, TGA, and WAXS. The hardwood lignin fractions have a high content of C5-substituted OH groups. The WAXS studies on lignin fractions revealed the presence of two π-π stacking conformations, sandwiched (4.08–4.25 Å) and T-shaped (6.52–6.91 Å). The presence of lignin superstructures with distances/sizes between 10.5 and 12.8 Å was also identified. The curing reaction of the thermosets was investigated by RT-FTIR. Almost all thermosets (excepting one fraction) reached 95% of the thiol conversion in less than 17 h, revealing the enhanced reactivity of the allylated hardwood lignin samples. The mechanical properties of the thermosets were investigated by DMA. The curing performance, as well as the final thermoset properties, have been correlated to variations in chemical composition and morphological differences of lignin fractions. The described results clearly demonstrate that technical hardwood lignins can be utilized for these applications, but also that significant differences compared to softwood lignins have to be considered for material design

Beam modelling and hardware design of an imaging heavy ion beam probe for ASDEX Upgrade

The imaging heavy ion beam probe (i-HIBP) developed at the ASDEX Upgrade tokamak is a new diagnostic concept for investigations at the edge of high temperature plasmas. By means of a heavy alkali beam injector, a neutral primary beam of an energy of 70 keV is injected into the fusion plasma, where it is ionized generating a fan of secondary beams. These are deflected by the magnetic field of the tokamak and intersect a scintillator plate in the limiter shadow of the tokamak. The light pattern on the scintillator detected with a high speed camera contains radial information on the density, electrostatic potential and the magnetic field in the edge region of the plasma. For the design of the i-HIBP, a detailed beam model including the 3D tokamak magnetic field and beam attenuation effects for cesium and rubidium atoms is developed in order to find the optimum injection scheme within the limited space of the tokamak environment for maximum signal intensities. Based on the optimized injection, the arrangement of the injector outside the vacuum-vessel and the detailed design of the optical in-vessel system is determined.Helmholtz Association grant no. VH-NG-135

Design of Hygroscopic Bioplastic Products Stable in Varying Humidities

Hygroscopic biopolymers like proteins and polysaccharides suffer from humidity-dependent mechanical properties. Because humidity can vary significantly over the year, or even within a day, these polymers will not generally have stable properties during their lifetimes. On wheat gluten, a model highly hygroscopic biopolymer material, it is observed that larger/thicker samples can be significantly more mechanically stable than thinner samples. It is shown here that this is due to slow water diffusion, which, in turn, is due to the rigid polymer structure caused by the double-bond character of the peptide bond, the many bulky peptide side groups, and the hydrogen bond network. More than a year is required to reach complete moisture saturation (approximate to 10 wt.%) in a 1 cm thick plate of glycerol-plasticized wheat gluten, whereas this process takes only one day for a 0.5 mm thick plate. The overall moisture uptake is also retarded by swelling-induced mechanical effects. Hence, hygroscopic biopolymers are better suited for larger/thicker products, where the moisture-induced changes in mechanical properties are smeared out over time, to the extent that the product remains sufficiently tough over climate changes, for example, throughout the course of a year

Ionising radiation metrology for the metallurgical industry

Every year millions tons of steel are produced worldwide from recycled scrap loads. Although the detection systems in the steelworks prevent most orphan radioactive sources from entering the furnace, there is still the possibility of accidentally melting a radioactive source. The MetroMetal project, carried out in the frame of the European Metrology Research Programme (EMRP), addresses this problem by studying the existing measurement systems, developing sets of reference sources in various matrices (cast steel, slag, fume dust) and proposing new detection instruments. This paper presents the key lines of the project and describes the preparation of radioactive sources as well as the intercomparison exercises used to test the calibration and correction methods proposed within the project.JRC.D.4-Standards for Nuclear Safety, Security and Safeguard